From Nanopowders to Functional Materials

166 Pages·2005·21.282 MB·166\166

by  Piticescu, Radu Robert, Lojkowski, Witold, Blizzard, John R. (Eds.)

A
From Nanopowders to
Functional Materials

Proceedings of Symposium G
European Materials Research Society
Fall Meeting
Warsaw University of Technology
th th
6 -10 September, 2004
Edited by
Radu Robert Piticescu, Witold Łojkowski
and John R. Blizzard

TRANS TECH PUBLICATIONS LTD

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A
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Volume 106 of
Solid State Phenomena
ISSN 1012-0394
(Pt. B of Diffusion and Defect Data - Solid State Data (ISSN 0377-6883))
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A
E-MRS FALL MEETING 2004 – SYMPOSIUM G

FROM NANOPOWDERS TO FUNCTIONAL MATERIALS

Introduction

Research and development in the whole area of nanomaterials including – thin films, nanowires,
nanocrystals, nano-composites and nanostructured bulk materials – is continuing to increase year by
year. More and more attention is being focused on research to enable greater control of the
structure at nanometer level in order to ensure that the desired functional properties can be
obtained.

The symposium aim was to enable those working at the leading edge of research to present and
debate the progress being made in the theory and applications of functionalised nanoparticles within
a multidisciplinary topic.

Applications of functional materials based on their mechanical, catalytic, electronic, optical and
photonic properties, atomic and transport properties, electrical, magnetic and ferroelectric
properties as well as biocompatibility presented in this symposium are expected to innovate the
nanotechnologies of tomorrow.

As part of the symposium a Joint Session was held with Symposium I – Metal Based
Nanomaterials, Thin Films and Surfaces. This volume includes the abstracts of this Joint Session as
well as the abstracts of the Plenary Session.

Radu Robert Piticescu
Witold Łojkowski
John R. Blizzard

The Symposium Organisers

Radu Robert Piticescu, Institute for Non-Ferrous and Rare Metals, Bucharest, Romania
e-mail: [email protected]

Witold Lojkowski, Institute for High Pressure Physics, Polish Academy of Sciences, Warsaw, Poland
e-mail: [email protected]

Claude Monty, Procédés, Matériaux et Energie Solaire (PROMES), Font Romeu, France
e-mail: [email protected]
A
Table of Contents
Luminescence Properties of Neodymium-Doped Yttrium Aluminium Garnet Obtained by
the Co-Precipitation Method Combined with the Mechanical Process
E. Caponetti, M.L. Saladino, D. Chillura Martino, L. Pedone, S. Enzo, S. Russu, M. Bettinelli and
A. Speghini 7
High-Pressure Induced Structural Decomposition of RE-Doped YAG Nanoceramics
D. Hreniak, S. Gierlotka, W. Łojkowski, W. Stręk, P. Mazur and R. Fedyk 17
Formation of Core-Shell Nanoparticles by Laser Ablation of Copper and Brass in Liquids
P.V. Kazakevich, A.V. Simakin, V.V. Voronov, G.A. Shafeev, D. Starikov and A. Bensaoula 23
Laser-Induced Size and Shape Transformation of Silver Colloidal Nanoparticles
N. Tarasenko, A. Butsen, G. Shevchenko and I. Yakutik 27
Direct Electrochemical Activity and Stability of Capped Platinum Nanoparticles
S. Cavaliere, F. Raynal, A. Etcheberry, M. Herlem and H. Perez 31
Precipitation of Nickel Hydroxides from Nickel Dodecylsulphate
C. Coudun and J. Hochepied 35
Microstructural Characterization of BaTiO Ceramic Nanoparticles Synthesized by the
3
Hydrothermal Technique
X.H. Zhu, J.M. Zhu, S.H. Zhou, Z.G. Liu, N.B. Ming and D. Hesse 41
Hybrid HAp-Maleic Anhydride Copolymer Nanocomposites Obtained by In Situ
Functionalisation
R.M. Piticescu, G.C. Chitanu, M. Albulescu, M. Giurginca, M.L. Popescu and W. Łojkowski 47
Review on the Production and Synthesis of Nanosized SnO
2
S. Papargyri, D.N. Tsipas, D.A. Papargyris, A.I. Botis and A.D. Papargyris 57
Phase Stability in Nanocrystalline Zirconia
G. Baldinozzi, D. Simeone, D. Gosset and M. Dutheil 63
Natural Opal as a Model System for Studying the Process of Biomineralization
L. Pramatarova, E. Pecheva, R. Presker, U. Schwarz and R. Kniep 75
New Nano-Sized Sensing Drug and Its Clinical Application
R. Ion and D. Brezoi 79
Nanostructure, Nanochemistry and Grain Boundary Conductivity of Yttria-Doped Zirconia
A. Rizea, J.M. Raulot, C. Petot, G. Petot-Ervas and G. Baldinozzi 83
Wavelength Tunable Random Laser
E. Tikhonov, V.P. Yashchuk, O. Prygodjuk and V. Bezrodny 87
Potential of Nano-Sized Rare Earth Fluorides in Optical Applications
U.H. Kynast, M.M. Lezhnina and H. Kätker 93
Luminescence of ZrO Nanocrystals
2
D. Millers, L. Grigorjeva, W. Łojkowski and A. Opalińska 103
Additional Absorption in the Multiply Scattering Absorbing Media
V.P. Yashchuk, E. Tikhonov, O. Prygodjuk, O. Levandovska and M. Zhuravsky 109
Lateral Size of Self-Patterned Nanostructures Controlled by Multi-Step Deposition
I. Szafraniak, D. Hesse and M. Alexe 117
Hydroxyapatite Growth on Glass/CdSe/SiO Nanostructures
x
L. Pramatarova, E. Pecheva, D. Nesheva, Z. Aneva, A.L. Toth, E. Horváth and F. Riesz 123
Spectroscopic Ellipsometry and Raman Studies on Sputtered TiO Thin Films
2
B. Karunagaran, Y.K. Kim, K.H. Kim, S.K. Dhungel, J.S. Yoo, D. Mangalaraj and J. Yi 127
Formation of Thallium Sulphide Layers on Polyethylene (PE) Sulphurised in a Solution of
Higher Polythionic Acid
I. Bružaitė, V. Janickis, I. Ancutienė and V. Snitka 133
Polymer Matrix Composites with Particles of TiC Obtained by a Sol-Gel Method
K. Konopka, A. Biedunkiewicz, A. Boczkowska , Z. Rosłaniec and K.J. Kurzydłowski 141
Self-Organization and Dynamic Characteristics Study of Nanostructured Liquid Crystal
Compounds
N.V. Kamanina, Y.A. Zubtsova, V.A. Shulev, M.M. Mikhailova, A.I. Denisyuk, S.V. Butyanov,
S.V. Murashov and I.Y. Sapurina 145
b From Nanopowders to Functional Materials
CBN Composites with a Nanosized Binding Phase
W. Gorczyńska-Zawiślan, E. Benko and P. Klimczyk 149
Microstructure and Mechanical Properties of Spark Plasma Sintered
ZrO -Al O -TiC N Nanocomposites
2 2 3 0.5 0.5
K. Vanmeensel, K.Y. Sastry, J. Hennicke, G. Anné, D. Jiang, A.I. Laptev, J. Vleugels and O. Van
der Biest 153
Effect of Sintering Temperature on Structure and Properties of Al O /Ni-P Composites
2 3
with Interpenetrating Phases
J. Michalski, M.J. Woźniak, K. Konopka, J. Bielinski, S. Gierlotka and K.J. Kurzydłowski 161
Plenary Session Abstracts 167
Joint Session Abstracts 173
A
Luminescence Properties of Neodymium-doped Yttrium Aluminium
Garnet Obtained by the Co-precipitation Method Combined with the
Mechanical Process

E. Caponetti1, M.L. Saladino1, D. Chillura Martino1, L. Pedone1, S. Enzo2,
S. Russu2, M. Bettinelli3 and A. Speghini3

1Dipartimento di Chimica Fisica “F. Accascina”, Università di Palermo, Viale delle Scienze Parco
D'Orleans II, pad.17, I-90128 Palermo (ITALY)
2Dipartimento di Chimica, Università di Sassari, via Vienna n. 2, I-07100 Sassari (ITALY)
3Dipartimento Scientifico e Tecnologico, Università di Verona, Ca' Vignal 1, strada le Grazie 15, I-
37134 Verona (ITALY)

Keywords: Nd:YAG, nanoparticles, coprecipitation, Ball Milling, X-ray diffraction, luminescence

Abstract. Nanopowders of yttrium aluminium garnet Y Al O (YAG) doped with neodymium
3 5 12
ions were obtained by the co-precipitation method from the reaction of aluminium and yttrium
nitrate and neodymium oxide with ammonia. After washing and drying the hydroxide precursors
were calcined at 500, 700, 800 and 900 °C for 1 hour and at 1000 °C for 3 hours. This product
was treated by ball milling in a zirconia vial for 0.5, 1.5 and 10 h in order to achieve smaller
nanoparticles. The structure, microstructure, morphology and optical properties were investigated
by means of diffractometric, microscopic and spectroscopic techniques. The course of the
amorphous-to-crystalline transformation was complete after calcining the powder for 1 hour at 900
°C.

In the sample calcined for 3 hours at 1000 °C, the mean size of crystallite microdomains was
reduced from 600 Å to 300, 250 and 160 Å after 0.5, 1.5 and 10 h of mechanical treatment
respectively. The treated product was found to be contaminated with ZrO . This contamination,
2
from the vial and hardened ZrO balls reaches ca. 30 wt % after 10 h of mechanical treatment but
2
causes only a slight reduction of the neodymium luminescence life-time, thus maintaining
significant applicative properties.

Introduction

Compounds of the Y O -Al O phase diagram represent one of the most important classes of hosts
2 3 2 3
for luminescence applications [1]. The compound 3Y O ·5Al O best known as yttrium
2 3 2 3
aluminium garnet Y Al O (YAG), when doped with Nd3+ ions, constitutes one of the most widely
3 5 12
used laser active materials [2]. It has high thermal conductivity, hardness, and chemical stability
and is attractive from a physical viewpoint as it is transparent in the range from ultraviolet to the
mid infrared. Further, the properties obtained by luminescent powder materials have aroused
interest for their possible use in plasma display panels, field emission displays and cathode ray
targets [3-6]. It is clear that, in addition to luminescent properties, particle size and morphology of
the garnet powder play an important role with respect to resin incorporation and optical behaviour.
Generally the synthesis technique consists in firing the reactants at high temperature to obtain
oxides that are subsequent subjected to intensive milling to obtain the desired particle size
distribution [7]. The limitations of this procedure in the case of luminescence are known because
of the impurities introduced from the milling tools [8].

Utilizing advanced precipitation techniques enables the required particle characteristics to be
obtained whilst at the same time overcoming the limitations of milling [9]. One further possibility
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8 From Nanopowders to Functional Materials
for fine processing of luminescent materials is to combine the chemical advanced synthesis with
the mechanical process, that is preparing relatively fine particles of garnets and then milling in a
suitable vial made of oxides, such as Al O (corundum) or ZrO (zirconia), which do not interfere
2 3 2
substantially with the optical properties. The aim of this investigation was to assess this method
even undertaking prolonged mechanical processing, for which contamination may become
important.

In this paper we present the structural and optical characterization of Nd Y Al O powders,
0.15 2.85 5 12
obtained by the co-precipitation method, before and after milling with colliding bodies (vial and
balls) made of hardened ZrO .
2

Experimental

Materials

The materials used were Y(NO ) ·6H O (Aldrich, 99.9%), Al(NO ) ·9H O (Aldrich, 98%) and
3 3 2 3 3 2
Nd O (Sigma-Aldrich, 99.99%) were the sources of Y3+, Al3+ and Nd3+ ions, respectively, Nitric
2 3
acid (Aldrich, 90%) and Ammonia solution (E. Merck 25%). The solutions were prepared using
the chemicals in the as received condition and adding conductivity grade water.

Nd-YAG preparation

Nd:YAG was prepared by the co-precipitation method. Y(NO ) ·6H O and Al(NO ) ·9H O were
3 3 2 3 3 2
dissolved in deionised water and Nd O was dissolved in dilute nitric acid. Aqueous solutions of
2 3
yttrium, aluminium and neodymium nitrates were mixed in a Nd:Y:Al molar ratio of 0.15:2.85:5.
The hydroxides were precipitated by drop-wise addition of 5M ammonia solution into the solution
constant stirring until a pH of 8 was reached. The gelatinous precipitate was filtered and washed
with water and ethanol to remove residual ammonia and nitric ions. The precipitate was oven
dried at 50°C to obtain the precursor powder that was later calcined at 500, 700, 800 and 900°C for
1 hour and 1000°C for 3 hours, respectively[10,11]. The material produced by calcination at 1000
°C was mechanically treated for 0.5, 1.5 and 10 h respectively using a Spex mixer/mill model 8000
with colliding bodies (vial and balls) made of hardened ZrO . The powder, before and after each
2
mechanical treatment, was characterized by XRD, SEM, EDX, TEM and luminescence techniques.

Methods of Investigation

Powder X ray diffraction (XRD) patterns were recorded with two commercial diffractometers in
the Bragg Brentano geometry (Philips PW 1050/39 and a Bruker D8 diffractometer respectively)
using Cu K radiation (λ = 1.5418 Å). Both generators worked at a power of 40 kV and 30 mA.
α
The resolution of both instruments was determined using α-SiO and α-Al O standards. The
2 2 3
powder patterns were analyzed using the Rietveld method using the programme MAUD [12].

Scanning Electron Microscopy (SEM) analysis has been performed on a Philips XL30 equipped
with a EDX device. The accelerating voltage was 25 kV and the samples were supported on the
stubs by carbon paint and coated with gold.

A Tecnai 10 (FEI Company) operating at an accelerating voltage of 100 kV was used for the
Transmission Electron Microscopy (TEM) analysis. Samples were prepared by dispersing the
powder in ethyl alcohol and by sonicating the suspension for 10 minutes. A drop of the suspension
was placed on a 300 mesh grid.
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Solid State Phenomena Vol. 106 9
The luminescence spectra at room temperature in the near infrared range were measured exciting
with the 488.0 nm radiation of an Argon laser (Spectra Physics, mod 2017). The scattered signal
was analyzed by a half-meter monochromator equipped with a 150 lines/mm grating and a CCD
detector (Spectrum One, Jobin-Yvon). A fibre optic probe was employed. The Nd3+ ion
luminescence decay curves were measured under excitation with the third harmonic radiation (355
nm) of a Nd-YAG pulsed laser. The signal was detected using the above monochromator and a
cooled GaAs photomultiplier (Hamamatsu).

Results and Discussion

The phase evolution process of the powder calcined at various temperatures was followed by X-ray
diffraction. The sequence of patterns reported in Figure 1 show that the precipitate remains
completely amorphous to X-rays up to 500°C and appreciable crystallization seems to occur at 700
°C for the heat treatment conditions adopted. After heat treatment at 900°C, Nd:YAG appeared
completely crystallized in the morphology of the garnet cubic Y Al O phase.[10]
3 5 12

900 °C 100% crystalline
n.
u
b. 800°C 45.6% Amorphous
r
a
y \
sit
n
e
nt Figure 1. XRD diffraction patterns
I
for hydroxides precursor calcined
700°C 74.8% Amorphous
for 1h at the quoted temperatures.
Data points are from the
experiment, full lines refer to the
Rietveld refinement. The so-called
500°C 100% Amorphous
crystallinity is also quoted.

20 40 60
Scattering angle 2θ

The amorphous-to-crystalline transformation of the powder material can be followed quantitatively
using the Rietveld method [13], provided that an “amorphous structure factor” is produced before
the refinement process. For this, analogous to the work of Le Bail [14], the study commenced with
the pattern of the sample calcined at 500°C which displayed the typical profile of an amorphous
substance. A monoclinic crystalline structure factor was then modified in terms of structural
parameters, e. g. fractional coordinates of atoms in the unit cell, and microstructural parameters,
e.g. reduced crystallite size and lattice disorder, until a satisfactory agreement with the experimental
data was obtained. The reliability of this procedure has been discussed in the case of ceramic
materials by Lutterotti and co-workers [15] and relies mainly on its ability to fit the diffuse haloes
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10 From Nanopowders to Functional Materials
of the diffraction pattern while keeping “reasonable” interatomic distances coupled with the correct
atomic density in the unit cell. The amorphous structure factor was used in the subsequent patterns
of specimens treated at 700 and 800 °C respectively. As can be seen in figure 1, calcining the
sample at 700 °C separates ca 25 mol% of crystalline Y Al O , at the expense of the remaining
3 5 12
amorphous matrix. The Y Al O phase becomes predominant at 800°C, though the specimen is
3 5 12
still “semicrystalline”, and at 900°C the crystallization process appears totally complete, since no
discernible amorphous component can be detected above the background base line.

The evolution of these patterns is similar to those observed for pure YAG powders prepared by
pyrolysis of metallorganic precursors [16], by a citrate gel method [17] and by a carbonate
precursor via the coprecipitation method from a mixed solution of ammonium aluminium sulphate
and yttrium nitrate [18].

Hreniak et al. [5,19] have reported XRD patterns of YAG powders with a Nd/Y ratio 0.05 in the
temperature range 800–1400 °C, suggesting that the materials are completely crystalline after
calcining at 800 °C for 16 hours. Moreover, the average crystallite size estimated using the
Scherrer equation [20] turned out to be about 250 Å which is consistent with the result of <d> =
300 Å on the specimen treated at the same temperature. It is worth noting that the latter figure is
obtained after separating the lattice strain component from the total broadening observed for all the
garnet peaks of our pattern.

XRD powder patterns (log scale) of the Nd:YAG specimen calcined at 1000 °C and mechanically
treated for the times quoted are reported in Figure 2. By comparing the peak positions of the lower
pattern with the calculated bar sequence of YAG reported at the bottom of figure 2, it can be
surmised that the specimen is entirely YAG single phase.

Rwp=6.52%
10 h BM

Rwp=7.01%
1.5 h BM Figure 2. XRD patterns of the Nd:YAG

samples calcined at 1000 °C and

mechanically treated for the times

b. un. R0.w5p h= 7B.0M6% qbuetowteede.n T ehxep aegrirmeeemnteanl td faatcat opro iRnwtsp and
ar
y\ calculated curve is also reported. For the
sit
n definition of R see ref. 13
e wp
y int Rasw pp=re1p0a.4re4d%
a
r
-
x

Nd-YAG
m-ZrO2
t-ZrO2

40 80

Scattering angle 2θ
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Solid State Phenomena Vol. 106 11
The structure of pure YAG is cubic, space group Ia-3d (# 230 in the Int. Tables), 8 stoichiometric
units in the cell (Z=8) and with the unit cell edge a, which is reported several times in the
Inorganic Crystal Structure Database ICSD, with a scatter in the range between 12.000 Å and
12.024 Å [21]. From the technical point of view, the evaluation of the lattice parameter is made
very precisely with the Rietveld method because the programme accounts for possible
misalignment of the specimen in the Bragg-Brentano geometry, taking into consideration all the
hkl peaks in the data collection range simultaneously.

According to Cüneyt Tas [22], the addition of 1.1 at% Nd does not cause a detectable change,
either in the individual d-spacing, or the lattice parameter of the YAG structure, which, however,
was reported to be a = 12.053 Å. However, Garskaite et al. [23], in the case of 1.1 cationic % of
Er in YAG, reported the lattice parameter to be a = 12.245 Å. The refined value of the lattice
parameter a after the Rietveld analysis carried out in this work was shown to be 12.056 Å. This is
different by more than experimental uncertainty from that of pure garnet due to the partial
substitution for Y3+ sites with Nd3+ cations. Actually, an expansion of the unit cell is expected in
the case of a solid solution of Nd in the YAG structure, since the ionic radius of Yttrium is known
to be 0.90 Å, while that of Neodymium is 0.995 Å. In the absence of specific calibration studies of
the lattice parameter as a function of Nd concentration, it may be inferred that the content of Nd in
the specimen used may be close to that of Cüneyt Tas. In addition to this, assuming from the
preparation conditions that all cations are completely precipitated from the solution, it was inferred
that the largest possible cationic % of Nd is 0.15/8 = 1.875 % and if the oxygen atoms are taken
into account 0.75 at. % is obtained. It should then be interesting to systematically inspect the
effect of Nd addition in order to evaluate the lattice parameter expansion precisely and to probe the
degree of solubility of Nd atoms in the YAG matrix.

Regarding the line broadening effects, which are emphasized in Figure 1 and 2 because of the
logarithmic intensity scale, the correction from the instrument contribution gives an average
crystallite size of ca. 600 Å, which confirms the attainment of a nano range size by the synthesis
procedure adopted. A moderate lattice strain ε = 0.0025 is also present. The error bar associated
with these quantities is generally assumed to be around 10-15%, but this is difficult to estimate
accurately for a number of reasons. Firstly, one assumes that the model adopted for the structure
and microstructure of the phase is correct. If this is true, then the distribution of residuals (i.e., the
difference between experimental and calculated values) would be uniform and normal. The
difference between the square root of experimental and calculated values is reported at the bottom
of Figure 2 for the specimen calcined at 1000 °C and shows that the residuals are far from normal,
in spite of the apparently “good” agreement between the model structure factor calculation and the
experiment. Specifically, a basic assumption is made in attributing the Cauchy-like component of
peak profiles to crystallite size effects, while the Gauss content of the peak is attributed to the
internal lattice strain ε. This assumption may be questionable in specific cases, but it is the best
that has been implemented in the majority of the Rietveld programs available.

Ball milling of the Nd:Y Al O phase for 30 minutes induces fragmentation of the crystallite
3 5 12
domains to about 300 Å in size, while the lattice strain remains substantially unchanged. The
lattice parameter of the cubic garnet slightly decreases to a = 12.045 Å. In addition to this, small
broad features can be perceived from the pattern, which are due to some contamination of ZrO
2
from the vial, about 3.5 wt%.

Prolonging the milling for 1.5 hours introduces further fragmentation of the YAG domains to an
average crystallite size of 250 Å, the lattice microstrain being unchanged. The contamination from
ZrO is evaluated as 9.0 wt.%. Finally, the upper pattern of Figure 2 displays the structure
2
obtained after 10 hours of ball milling. The lattice parameter remains at a value of 12.049 Å, the